Grease compositions containing synthetic gelling agents



United States Patent GREASE COMPOSITIONS CONTAlNING SYNTHETIC GELLINGAGENTS John J. Giammaria, Woodbury, N. J., assignor to Socony- VacuumOil Company, Incorporated, a corporation of New York No Drawing.Application September 27, 1952, Serial No. 311,960

19 Claims. (Cl. 252-33.6)

The present invention has to do with grease compositions and, morespecifically, has to do with grease compositions containing metal saltsof reaction products obtained by reaction of alcohols or amines withacidic copolymers of alpha, beta unsaturated polycarboxylic acids ortheir anhydrides with low molecular weight compounds having a terminalvinyl group (--CH=CH2).

This application is a continuation-in-part of application Serial No.215,859, filed March 15, 1951. In said application, description was madeof a novel group of grease compositions, namely, greases containingmetal salts of acidic copolymers of said acids or anhydrides withcertain aliphatic compounds having a terminal vinyl group. The aliphaticcompounds used in preparing said copolymers are alpha olefins, RCH=CH2,and allyl esters, RCOOCHzCH=CI-I2, in both of which R is an alkyl grouphaving at least and up to carbon atoms. Coupled with this discovery isthe related discovery that when low molecular weight vinyl compounds,such as propylene, styrene, vinyl acetate and the like, arecopolymerized with the aforesaid acids or anhydrides, and the copolymers(1) thereof are, in turn, converted to their corresponding metal saltsor soaps, the soaps are too insoluble for use as grease gelling agents.Now, however, it has been further discovered that said copolymers (I)can be reacted with certain alcohols or amines, and the reactionproducts thus obtained can be converted into metal soaps which aregelling agents of excellent character.

It is an object of this invention, therefore, to provide soaps ofpartial esters and partial amides of acidic copolymers of low molecularweight vinyl. compounds and of said alpha, beta unsaturatedpolycarboxylic acids. It is also an object of this invention to providegreases capable of withstanding severe operating conditions. It is alsoan object to provide greases effective for high temperature use, such asat 250-350 F. and higher. Other objects will be apparent from thefollowing description:

I. ACIDIC COPOLYMERS A. VINYL COMPOUNDS The vinyl compounds which can beused to form the acidic copolymers with the alpha, beta unsaturatedpolycarboxylic acids, are: aliphatic alpha olefins; allyl esters ofaliphatic acids; allyl ethers of aliphatic alcohols; vinyl esters ofaliphatic acids and vinyl ethers of aliphatic alcohols; andvinyl-substituted aromatic hydrocarbons. In particular, compounds of thegeneral formula,

wherein R, is hydrogen or an aryl, aralkyl, alkyl, alkaryl, cycloalkyl,ester or ether group, containing less than about ten carbon atoms, andcompounds of the general formula H2C=CHCH2R1, wherein R1 is as describedabove, can be used herein. In general, the vinyl com pounds havemolecular weights of less than about 200. Typical of such compounds are:styrene, vinyl toluene, vinyl naphthalene, ethylene, propylene,butylene, isobutylene, l-octene, vinyl acetate, vinyl butyrate, vinyl 2-ethylhexoate, vinyl methyl ether, vinyl butyl ether, vinyl octyl ether,allyl acetate, allyl butyrate, allyl Z-ethylhexoate, allyl methyl ether,allyl butyl ether and allyl octyl ether.

The allyl ethers can be either the allyl ethers of monohydric orpolyhydric alcohols, although the ethers of monohydric alcohols arepreferred. The preparation of 2,698,297 Patented Dec. 28, 1954 2 theseethers is well known, merely involving the reaction between an allylhalide and a sodium alcoholate. Thus, for example, allyl methyl ether,methallyl butyl ether, allyl amyl ether, allyl heptyl ether, methallylocty ether, allyl lauryl ether, allyl hexadecyl ether, methallyloctadecyl ether and the like can be used.

Illustrative of the allyl esters are allyl acetate, allyl propionate,allyl butyrate and allyl caproate. It is not necessary that single acidsbe used since mixtures of saturated and unsaturated monocarboxylic acidscan be used to prepare the allyl esters.

Derivatives of the vinyl compounds, or substituted vinyl compounds,which can be used herein, include: halogen-substituted materials such aschlorostyrene; alkoxy-substituted materials such as p-methoxy styrene;and alkyl-substituted materials such as alpha-methyl styrene. As will benoted from the character of the foregoing typical substituted vinylcompounds, substituted groups which can be present are those which donot interferewith the course of the copolymerization with the aforesaidacids or anhydrides. In other words, a substituent group which can bepresent in the vinyl com pound is one which is substantially inert orunreactive in the copolymerization. The substituent group, however,generally modifies the character of the final metal soap products; yet,in all cases, the metal soaps are characterized by satisfactorysolubility and gelling character. In connection with divinyl benzene,divinyl naphthalene and the like, which can be used as modifiers insmall amounts (e. g., 1-5 per cent) as vinyl compounds, it should benoted that these particular compounds are characterized by a high degreeof reactivity in view of the two vinyl groups.

It will be understood, of course, that mixtures of the aforesaid vinylcompounds, can be used in place of the individual reactant. Similarly,mixtures containing substantial, and preferably, major proportions ofone or more of said vinyl compounds can be used. Examples of suchmixtures are: a crude styrene containing ethyl benzene, and a crudebutylene containing butanes.

Particularly preferred herein of the vinyl compounds, in view of theiravailability, high reactivity and relatively low cost, are: styrene andvinyl acetate.

B. ALPHA, BETA UNSATURATED ALIPHATIC PoLYcARBoxLIc Acms Of the alpha,beta unsaturated aliphatic polycarboxylic acids the dicarboxylic acidsare preferred. Illustrative of the preferred dicarboxylic acidsaremaleic, fumaric, itaconic, glutaconic, mesaconic and citraconic, andthe tri-carboxylic aconitic acid. Of these, maleic acid in the form ofits anhydride is particularly preferred at this time because of itsready availability, cost and because it is highly reactive. It will berecognized by those skilled in the art that the anhydrides of the acidsor the acid halides as well as the acids having less than ten carbonacids per se can be used although generally it is preferred to use theanhydrides in the preparation of the copolymers.

C. CATALYSTS Suitable catalysts for the copolymerization of a vinylcompound and an alpha, beta acid of the character described above, areorganic peroxides such as benzoyl peroxide, di-tertiary-butyl peroxide,and lauroyl peroxide, and the hydroperoxides such as cumenehydroperoxide. These latter catalysts are somewhat less effective thanthe peroxides as catalysts in this reaction. While peroxides are mostadvantageous catalysts, any of the wellknown polymerization catalystscan be used herein.

D. COPOLYMERIZATION CONDITIONS The copolymerization of the aforesaidvinyl compounds and acids (or anhydrides) is accomplished by heatingsubstantially equi-molar quantities of the reactants at temperatureswithin the range of about C. to about 150 C. in the presence of about0.1 to about 5.0 per cent of peroxide catalyst. Reaction time will varyfrom about a few minutes to several hours depending on temperature andmode of addition of peroxide. In the case of gaseous monomers, thereaction is run under pressure, e. g., -1000 pounds per square inch. Theamount of peroxide catalyst required, of necessity, will vary with thetype of vinyl compound used. Thus, for example, 0.5 to 1.0 per cent ofperoxide catalyst is sufiicient when a vinyl ester or vinyl ether isused; whereas, about 2.0 to about 3.0'per cent of peroxide catalyst isrequired when-an alpha olefin or an allyl-ester is used. Thecopolymerization can be carried out in the presence or absence of asolvent. Suitable solvents are toluene, xylene, dioxane, highlyacid-refined mineral oil such as white oil and the like. For-the purposeof commercial grease-making, the vinyl'compound and the acid oranhydride can be copolymerized in a suitable pressure kettle, then theresulting copolymer can be converted to the corresponding partial esteror partial amide, and the latter thus obtained can be diluted with hotmineral'oil of the required viscosity at the completion of the reactionwith the alcohol or amide.

E. STRUCTUREOF ACrDIC CoroLYMEns acid in the anhydride form:

O\ /O\ /O CHCHz-C I (3H2 H H R 11,

wherein R is the alkyl residue of an olefin, an allyl ester or an allylether, i. e., R is R, RO and RCOO, and R is an alkyl group or the alkylresidue of a vinyl ether or ester.

It has been found that the value of n in the formula given above for theacidic copolymer is alarge whole number. That is, the average molecularweight of the acidic copolymers from which the present gelation agentsare prepared is about 1000 to about 100,000, and preferably about 5000to about 50,000.

II. REACTION- PRODUCTS OF ACIDIC COPOLY- MERS WITH ALCOHOLS OR AMINES A.ALCOHOLS AND AMINES As indicated above, the acidic copolymers are.reacted with certain alcohols or with certain amines, and the reactionproducts thus obtained are converted, in turn, to their correspondingmetal salts. It has been determined that from about fifty to aboutninety per cent of the carboxyl groups of the acidic copolymers shouldbe reacted with an alcohol or amine, the percentage varying with theindividual alcohol or amine which is used. For example, a lowerpercentage of an alcohol or amine is required when a high molecularweight alcohol or amine is-used; Thus, from about ten to about fifty percent of the carboxyl groups of the acidic copolymer should be availablefor conversion to the corresponding metal salt groups.

It will be recognized that the acidic copolymers, whenreacted withalcohols, are converted to esters; and, when reacted with amines, areconverted to amides. Inasmuch as only a portion of the carboxyl groupsof the acidic copolymers are so converted, the resulting prodnets arepartial esters and partial amides, respectively.

The alcohols and amines used herein are monohydric audmonoamino in.character, contain at least abouteight carbon atoms per molecule, andare aliphatic; In general, primary aliphatic alcohols and aminescontaining from about ten to about eighteen carbon atoms per moleculeare preferred. Representative compounds include: alcohols such as octyl,decyl such as n-decanol, dodecanols such as n-dodecanol, tetradecanolssuch as n-tetradecanol, hexadecanols such as n-hexadecanol, octadecanolssuch as n-octadecanol, oleyl alcohol, Lorol 5-'wh1ch. contains a mixtureof C to C18 alcohols; am-

ines such as octyl, decylamines such as n-decylamine, dodecylamines suchas n-dodecylamine, hexadecylamines such as n-hexadecylamine,octadecylamines such as noctadecylamine and octadecenyl amine.

Particularly preferred herein of the alcohols is a mixture of C10 to C18alcohols containing a predominant amount of C12 alcohol; and of theamines is a mixture of C3 to C18 amines predominating in C18 amines.

B. REACTION CONDITIONS Reaction of an acidic copolymer and an alcohol oramine is effected by heating regulated quantities thereof at atemperature from about 200 to about 300 F. for about 1-3 hours. Aspreviously mentioned, the quantity of alcohol or amine so reacted islimited such that at least about fifty per cent of the carboxyl groupsof the acidic copolymers are converted to the corresponding respectiveester or amido group, and such that not more than about ninety per centof the carboxyl groups are so converted. Reaction is aided by using asmall amount, as one to two per cent based upon the quantity ofcopolymer and alcohol, of a catalyst such as sulfuric acid orparatoluene sulfonic acid. A solvent such as methyl ethyl ketone,toluene or xylene can also be used.

III. METAL SALT GELLING AGENTS A. METALS As has been statedhereinbefore, the novel gelation agents of this invention are metalsalts of the above-described partial esters and partial amides. Suitablemetals for the preparation of these gelling agents are the membersofgroups I to IV of Mendelee'lfs periodic system. In general, salts of themetals of groups I, II and III of such system, including lithium,calcium, barium and aluminum salts are preferred. Other typical metalsare: sodium, potassium, magnesium, zinc, strontium, indium, tin, leadand titanium.

B. REACTION CoNDITIoNs Any of the standard methods for the preparationof salts of organic acids can be used. For example, the partial ester orpartial amide can be neutralized with the hydroxide or alcoholate of themetal desired or the alkali metal or ammonium salt of the partial esteror partial amide can be reacted with the chloride, hydroxide, carbonateor other salt of the metal the final salt of which is sought. As ageneral but by no means sole procedure, about ten to about twenty-fiveper cent of the partial ester or partial amide is blended in a mineraloil of suitable viscosity, the amount of metal hydroxide or oxiderequired to neutralize all of the carboxyl groups of the partial esteror partial amide is added to the blend and the mixture is heated, whileagitating the same, to about 300 F. to about 500 F. The mixture is heldin this temperature range for about one-half to about three hours. Theresulting grease is cooled with or without agitation in a grease kettleor drawn off into pans to cool.

C. STRUCTURE In the light of the foregoing it is manifest'tha't thesalts of the aforesaid partial esters and partial amides will haveobvious but various structures dependent upon such factors as: (l) thevalence of the metal of the salt, (2) the presence of more than oneacidic component in the reaction mixture during the formation of thesalt and (3) the presence and valence of more than one metal in thereaction mixture during the formation of the salt. Thus, by way ofillustration, when making the salt of a monovalent metal and a mixtureof partial esters, the resulting gelation agent will be a mixtureofrnonoval'e'ntmetal salts of the various partial esters. Such a mixturecan. contain, for example, the following salt derived from a partialester:

wherein R and R are alkyl Correspondingly, a mixture can contain thefollowing salt derived from an amine:

wherein R is alkyl and R is hydrogen or alkyl In the foregoing formulae,M is the same or different monovalent metal of group I, and n is asdescribed above. It will be recognized, of course, that when polyvalentmetals of groups I to IV are used the resulting gelation agents are morecomplex since there can be cross linking of partial ester (or partialamide) units of separate copolymer chains through the polyvalentmetal aswell as simple neutralization of carboxylic acid groups of two partialester or amide units of the same copolymer chain by one atom of divalentmetal. The probable structures of the components of a gelation agentprepared from a trivalent metal such as aluminum are even more diverse.Therefore, it will be understood that the present gelation agents can beof simple components or a plurality of components dependent upon thepresence of: (1) one or more metals of single valence, (2) one or morepartial esters and/or partial amides, (3) a polyvalent metal and one ormore partial esters and/or partial amides, and (4) a plurality ofmonoand/or polyvalent metals and a plurality of partial esters and/orpartial amides.

Thus, greases containing, for example, a lithium-barium salt of apartial ester or a lithium salt of one partial ester and a barium saltof a second partial ester, can be prepared.

It has also been found that greases having a smooth texture can beprepared by converting a mixture of a partial ester (or partial amide)and a fatty acid to metal salts thereof in the oleaginous vehicle.Mixtures of a partial ester (or partial amide), a high molecular weightfatty acid and a low molecular weight fatty acid, can also be convertedto their corresponding metal salts, thereby making available excellentgreases of smooth texture. For example, a mixture of a partial ester anda fatty acid such as stearic or hydrogenated fish oil fatty acids can beused; so too can a mixture of a partial ester, a high molecular weightacid such as stearic or hydrogenated fish oil fatty acids and a lowmolecular weight fatty acid containing less than about six carbon atoms,preferably acetic acid. Fatty acids suitable for such purposes are theindividual fatty acid or mixtures of fatty acids or hydroxy fatty acidshaving about ten to about twenty-two carbon atoms in the molecule, suchas capric, lauric, stearic, hydroxy-stearic and hydrogenated fish oilfatty acids. The partial ester (or partial amide) and fatty acid arereacted with a single metal compound or a plurality of compounds of aplurality of metals of groups I to IV.

D. METHOD OF PREPARATION A general over-all procedure for preparing thegelling agents and greases of this invention is the following: Maleicanhydride and a vinyl compound are copolymerized in the presence of anorganic peroxide, and in a solvent such as toluene. An alcohol or amineis added to the reaction mixture, and the resulting mixture is heated inorder that a partial ester or partial amide be formed. The mixture thusobtained is dissolved in a quantity of mineral oil such that the metalgelling agent will be present in the oil in the desired concentration,e. g., fifteen to twenty per cent by weight. The hydroxide of thedesired metal, in an amount based upon the acidity of the partial esteror partial amide, is added and the resulting reaction mixture is heatedin order to form the gelling agent (or soap) and grease.

IV. ILLUSTRATIVE EXAMPLES Several illustrative but non-limiting examplesof some specific gelling agents and greases containing the same are setforth below.

EXAMPLE I Ten parts by weight of a styrene-maleic anhydride copolymer(kinematic viscosity of a ten per cent solution 6 in methyl ethylketone, 3.53 centistokes at 77 F.) were dissolved in parts by weight ofmethyl ethyl ketone, and 13.5 parts by weight of n-octadecanol wereadded. The resulting solution was heated at reflux (about 185 F.) forone hour. The solvent was gradually distilled off and was replaced withxylene, which was added gradually. The temperature of the reactionmixture was finally raised to 280 F. (elapsed time, about one hour), andwas kept at 280 F. for one hour. Xylene was then removed bydistillation. The resulting resinous product had a neutralization numberof 114.0, which indicates that the product is substantially the halfester of the n-octadecanol and the styrene-maleic anhydride copolymer.The partlial half ester has a theoretical neutralization number of Fourparts by weight of the partial ester were dissolved in twelve parts byweight of an acid-refined naphthenic oil having a viscosity of 232 S. U.S. at 100 F., and ten parts by weight of a solvent-refined naphthenicoil having a viscosity of 514 S. U. S. at 100 F. Three tenths part byweight of Ca(OH)z was added to the oil and the resulting mixture wasstirred and was heated to 320 F. (during one-half hour) and kept at 320F. for one hour. The resulting gel was cooled and milled to a smoothgrease. The grease contained about 15.4 per cent of soap.

EXAMPLE II Sixty parts by weight of styrene and 40.0 parts by weight ofmaleic anhydride were dissolved in 900 parts by Weight of toluene. Theresulting solution was heated to F. and 1.0 part by Weight of benzoylperoxide was added. Heating was continued to about 200 F. where reactiontook place as evidenced by clouding of the solution. Heating at reflux(about 220 F.) was continued for one hour. Ninety-eight parts by weightof lorol 5 alcohol (a mixture comprising 2.8% n-decanol, 61.0%n-dodecanol, 21.0% n-tetradecanol, 11.0% n-hexadecanol and 2.2%n-octadecanol) and 3.96 parts by weight of para-toluene sulfonic acidwere added. The mixture was heated at reflux for about 2 hours afterwhich the solvent was removed by distillation. The resinous partialester had a neutralization number of 123.0 (theoretical value, 144 N.N.).

Eighty parts by weight of the partial ester from above, 450.0 parts byweight of a solvent-refined naphthenic oil having a viscosity of 514 S.U. S. at 100 F., 6.5 parts by weight of Ca(OH)z and 10 parts by weightof water were mixed in a suitable grease kettle and heated to 335 F.over a four hour period. The grease was cooled to room temperature whilestirring. The final soap concentration was 15.6 per cent.

EXAMPLE III Eighty parts by weight of a partial ester (N. N., 101) of astyrene-maleic anhydride copolymer and n-octadecanol, prepared in thesame manner as the partial ester described in Example II, 360 parts byweight of a solvent-refined naphthenic oil having a viscosity of 514 S.U. S. at 100 F., 23 parts by weight of Ba(OH)2.8H2O and 10 parts byweight of water were mixed in a grease kettle and heated to 350 F.during a four hour period, and were maintained at 350 F. for a one hourperiod. The resulting grease was then stirred while it was cooled toroom temperature (about 7080 F.). The soap concentration of the greasewas twenty per cent.

EXAMPLE IV Seventy-three and one-half parts by weight of styrene, 49parts by weight of maleicanhydride and 1.23 parts by weight of benzoylperoxide were reacted at 150220 F. for one hour, in 1000 parts by weightof toluene as described in Example II, above. The styrene-maleicanhydride copolymer thus formed was partially esterified with a mixtureof 93.6 parts by weight of Lorol 5 alcohol and 9.9 parts by weight ofn-octadecanol, using 4.54 parts of paratoluene sulfonic acid ascatalyst, at 300 F. for two hours. The resulting partial ester had aneutralization number of 121.0.

Eighty parts by weight of the partial ester from above, 371 parts byweight of an acid-refined naphthenic oil (232 S. U. S. at 100 F.) and8.7 parts by weight of LiOI-LHzO dissolved in 78.0 parts by weight ofwater, were mixed in a suitable grease kettle and heated to 400 F. overa four hour period. The resulting grease was stirredWllllCTCOOllIlg-lOIOOIH temperature (80f The soap concentration, was18.0 per cent.

EXAMPLE V- Twenty-eight parts by weight of a propylene-maleic anhydridecopolymer, 48 parts by weightv of Lorol alcohol and 1 part. by weight'ofparatoluene sulfonic acid were reacted in 500.0 parts by weight ofdioxane,- as described in Example I to form azpartial ester of thecopolymer having a neutralization number of 137.0.

Six parts by weight:of the above partial ester, 24 parts by Weight of anacid-refined naphthenic oil, 2.66 parts by weight of Ba(OI-I)2.8HzO and2.0 parts by weight of water, were mixed and heated to.400 F. over a oneand one-half hour period. The resulting grease was stirred while coolingtoroom temperature. The grease contained 22.0 per centsoap.

EXAMPLE VI Forty-three parts by Weight of freshly distilled vinylacetate and 49.0 parts by weight of maleic anhydride were copolymerizedin 700 parts-by weight of dioxane using 1.0 part by weight of benzoylperoxide as catalyst at 150 F. for ten minutes. The resulting copolymerwas partially esterified witha mixture of 120 parts by weight of Lorol 5alcohol and 27 parts by weight of n-octadecanol, at 200 F. for sixhours, then to 350 F. for one-half hour, as described in Example I. Thepartial ester had a neutralization number of 102.0.

Six parts by weight of the above partial ester, 24 parts by weight of asolvent-refined naphthenic oil, 2 parts by weight of Ba(OH)2.8H2O and 2parts by weight of water were mixed and heated to 400 F. over a one andone-half hour period. The resulting grease was stirred while cool ingtoroom temperature. The soap content was 22.0 per cent.

EXAMPLE VII Fifty parts by weight of vinyl n-butyl ether and 49.0 partsby weight. of maleic anhydride were copolymerized in 800 parts by weightof toluene using 1.0 part by weight of benzoyl peroxide as catalyst at150 F. for one-half hour. The resulting copolymer was then partiallyesterified with a mixture of 120.0 parts by weight of Lorol 5 alcoholand 27.0 parts by weight of n-octadecanol, as described in Example I.The resulting partial ester had a neutralization number of 84.0.

Four and one-half parts by weight of the above copolymer, 25.5 parts byweight of said acid-refined naphthenic oil, and 0.7 part by weight ofaluminum isopropoxide were mixed and heated to 300 F. over a one hourperiod.

The clear grease was cooled statically to room temperature and thenmilled to a clear, soft grease. The soap content was 15.0 per cent.

EXAMPLE VIII Two parts by weight of a styrene-maleic anhydridecopolymer, 3.2 parts by weight of Armeen HT (mixture of 25.0%n-hexadecylamine, 70.0% n-octadecylamine and 5.0% n-octadecenylamine,marketed by Armour and EXAMPLE IX Forty parts by weight of HydrofolAcids 150 (mixture of 0.5% myristic, 17.7% palmitic, 77.6% stearic, 1.0%arachidic and 3.2% oleic marketed by Archer- Daniels-Midland Company),66.6 parts by weight of a partial ester of a styrene-maleic anhydridecopolymer, similar to that described in Example II, 574.0 parts byweight of said acid-refined naphthenic oil and 44.0 parts by weight ofBa(OH)z.8H2O were mixed in a suitable grease kettle and heated to 350 F.over a four and onehalf hour period. The resulting grease was cooled toroom temperature and milled. The soap content was 18.0 per cent.

EXAMPLE X Thirty parts by weight of HydrofoU Acids 150, 50.0

parts-.by-weight. of a partial ester-q of a styrene=maleic=a k hydridecopolymer, similar to-that-described, in Example II, 4.4 parts by weightof acetic acid, 44.7 parts by weight of B3.(OH)2.,8H2O and 415.0 partsby weightgof said acidrefined naphthenic oil,weremixed and heated to 360F. over a three hour period. The resulting grease was stirred while;cooling to room temperature and cut back with oil (72zparts by weight)to 1'8'per cent soap concentration.

In general; the greases of this invention are characterized by highdropping points, which fact indicates their use for high temperatureapplications. The dropping points of the grease; described. arelisted-in ,the following table.

Table] Grease: Dropping point; F. Example I 500+ Example II. 375'Example III 400+ Example IV 280'. Example V 450+ Example VI 400+ ExampleVII; 308 Example VIII; 426 Example IX 414" Example X 415+ 1 A. S. T. M.Designation: Dv 566. 12

It is seen. that most ofthe greases shown in Table- I have droppingpoints above 400 F.

V. OIL, VEHICLES The oil vehicles or oleaginous vehicles of the greasesof this invention can vary considerably in character. In general,mineral oils used are those characterized by a viscosity (S. U. V.) ofgreater than about 40 seconds at F., preferably from about 60 to about6000 seconds at 100 F. In place of all or part of the mineral oilcomponent, other oils of lubricating viscosity can also be used. Suchoils include synthetic vehiclescompr-ising polymerized olefins, estersof aliphatic dibasic acids, esters of polyalcohols and monocarboxylicacids, silicones, silicate esters, esters of phosphorous-containingacids, fluorocarbons, etc. Typical of such synthetic oils are:polypropylene, polypropylene glycol, di-(2-ethyl hexyl) sebacate,di-(Z-ethyl hexyl) adipate, dibutyl phthalate, polyethylene glycoldi-(Z-ethyl hexoate), polymethylsiloxane. The synthetic vehicles aremost suitable for providing greases for use in aircraft, since many ofsuch greases retain their lubricating value over. a Wide temperaturerange, from about 100 F. to about 500 F.

VI. CONCENTRATIONv OF GELLING AGENT The gelation agents are generallyused in amounts ranging from about 5 to about 50 per cent by weight ofthe finished grease composition, depending upon the consistency desiredand the purpose for which the grease is designed. The concentration. ofsuch agent or soap will also vary with the type of soap and thecomposition and viscosity of the base oil. Preferably, however,- thequantity of gelling agent will fall within the range of ten totwenty-five per cent by weight.

VII., MODIFYING AGENTS It is to be understood that the greases of thisinvention can also contain other characterizing materials and fillers.

For example, the greases can contain antioxidants such The greases ofthis invention are suitable for a wide range of industrial applications.Some, for example, are suitable for use as multi-purpose automotivegreases, serving as chassis, wheel-bearing, Water-pump greaselubricants. Others are multi-purpose industrial greases serving asplain-bearing and antiafrietion greases. for

normally loaded and heavily loaded equipm nt In,

general, then, greases contemplated herein range from semi-fluid typessuitable as textile machinery lubricants, to solid block type greasesused in lubrication of machinery in steel mills, paper mills, cementmills, etc.

I claim:

l. A grease comprising an oleaginous vehicle and a salt in an amountsutficient to thicken said vehicle to form a grease, said salt being ametal salt of an acidic reaction product obtained by reaction of acompound selected from the group consisting of an aliphatic monohydricalcohol having at least about eight carbon atoms per molecule and analiphatic monoamine having at least about eight carbon atoms permolecule, with an acidic copolymer of an alpha, beta unsaturatedpolycarboxylic acid and a low molecular weight organic compound having aterminal vinyl group and having less than about ten carbon atoms permolecule, such that from about fifty to about ninety per cent of thecarboxyl groups of the acidic copolymer are reacted with said compound,said acidic copolymer having a molecular weight above about 1,000, themetal of said salt being selected from the group consisting of metals ofgroups I through III of Mendeleeffs periodic system.

2. A grease comprising an oleaginous vehicle, a salt (1) of a fatty acidhaving ten to twenty-two carbon atoms per molecule and a salt (2), in anamount sufficient to thicken said vehicle to form a grease, said salt(2) being a metal salt of an acidic reaction product obtained byreaction of a compound selected from the group consisting of analiphatic monohydric alcohol having at least about eight carbon atomsper molecule and an aliphatic monoamine having at least about eightcarbon atoms per molecule, with an acidic copolymer of an alpha, betaunsaturated polycarboxylic acid and a low molecular weight organiccompound having a terminal vinyl group and having less than about tencarbon atoms per molecule, such that from about fifty to about ninetyper cent of the carboxyl groups of the acidic copolymer are reacted withsaid compound, said acidic copolymer having a molecular weight aboveabout 1,000, the metal of said salt being selected from the groupconsisting of metals of groups I through III of Mendeleeffs periodicsystem.

3. A grease comprising an oleaginous vehicle, a salt (1) of a fatty acidhaving ten to twenty-two carbon atoms per molecule, a salt (2) of afatty acid having less than about six carbon atoms per molecule and asalt (3), in an amount sufficient to thicken said vehicle to form agrease, said salt (3) being a metal salt of an acidic reaction productobtained by reaction of a compound selected from the group consisting ofan aliphatic monohydric alcohol having at least about eight carbon atomsper molecule and an aliphatic monoamine having at least about eightcarbon atoms per molecule, with an acidic copolymer of an alpha, betaunsaturated polycarboxylic acid and a low molecular weight organiccompound having a terminal vinyl group and having less than about tencarbon atoms per molecule, such that from about fifty to about ninetyper cent of the carboxyl groups of the acidic copolymer are reacted withsaid compound, said acidic copolymer having a molecular weight aboveabout 1,000, the metal of said salt being selected from the groupconsisting of metals of groups I through III of Mendeleeffs periodicsystem.

4. A grease as defined by claim 1 wherein the low molecular weightorganic compound is an alpha olefin having less than about ten carbonatoms per molecule.

5. A grease as defined by claim 1 wherein the low molecular weightorganic compound is styrene.

6. A grease as defined by claim 1 wherein the polycarboxylic acid is adicarboxylic acid.

7. A grease as defined by claim 1 wherein the polycarboxylic acid is inanhydride form and is maleic anhydride.

8. A grease as defined by claim 1 wherein the monohydric alcohol is analiphatic alcohol having from about ten to about eighteen carbon atomsper molecule.

9. A grease as defined by claim 1 wherein the monm hydric alcohol is amixture of aliphatic monohydric alcohols having from ten to eighteencarbon atoms per molecule and predominantly dodecanol.

10. A grease as defined by claim 1 wherein the monoamine is an aliphaticamine having from about ten to about eighteen carbon atoms per molecule.

11. A grease as defined by claim 1 wherein the monoamine is a mixture ofaliphatic monoamines having from eight to eighteen carbon atoms permolecule and predominantly octadecylamine.

12. A grease as defined by claim 1 wherein the metal is an alkalineearth metal.

13. A grease as defined by claim 1 wherein the metal salt is present inan amount from about five to about fifty per cent by weight.

14. A grease as defined by claim 1 wherein the oleaginous vehicle is amineral oil having a viscosity from about to about 1000 S. U. S. at 100F.

15. A grease comprising a mineral oil of lubricating viscosity andcalcium salts in an amount suflicient to thicken said oil to form agrease, said salts being calcium salts of partial esters obtained byreaction of a mixture of aliphatic monohydric alcohols having from tento eighteen carbon atoms per molecule and predominantly dodecanol withan acidic copolymer of styrene and maleic anhydride having a molecularweight above about 1,000, such that about fifty per cent of the carboxylgroups of the acidic copolymer are reacted with said alcohols.

16. A grease comprising a mineral oil of lubricating viscosity and abarium salt in an amount sufiicient to thicken said oil to form agrease, said salt being a barium salt of a partial ester obtained byreaction of n-octadecanol with an acidic copolymer of styrene and maleicanhydride having a molecular weight above about 1,000, such that aboutfifty per cent of the carboxyl groups of the acidic copolymer arereacted with said alcohol.

17. A grease comprising a mineral oil of lubricating viscosity andbarium salts in an amount suflicient to thicken said oil to form agrease, said salts being barium salts of partial esters obtained byreaction of a mixture of aliphatic monohydric alcohols having from tento eighteen carbon atoms per molecule and predominantly dodecanol andoctadecanol with an acidic copolymer of vinyl acetate and maleicanhydride having a molecular weight above about 1,000, such that aboutfifty per cent of the carboxyl groups of the acidic copolymer arereacted with said alcohols.

18. A grease comprising a mineral oil of lubricating viscosity, bariumsalts (1) of a mixture of fatty acids having from sixteen to twentycarbon atoms per molecule and predominantly stearic acid and a bariumsalt (2), in an amount sufficient to thicken said oil to form a grease,said barium salt (2) being a barium salt of partial esters obtained byreaction of a mixture of aliphatic monohydric alcohols having from tento eighteen carbon atoms per molecule and predominantly dodecanol withan acidic copolymer of styrene and maleic anhydride having a molecularweight above about 1,000, such that about fifty per cent of the carboxylgroups of the acidic copolymer are reacted with said alcohols.

19. A grease comprising a mineral oil of lubricating viscosity, bariumsalts (1) of a mixture of fatty acids having from sixteen to twentycarbon atoms per molecule and predominantly stearic acid, barium acetate(2), and a barium salt (3), in an amount sufficient to thicken said oilto form a grease, said barium salt (3) being a barium salt of partialesters obtained by reaction of a mixture of aliphatic monohydricalcohols having from ten to eighteen carbon atoms per molecule andpredominantly dodecanol with an acidic copolymer of styrene and maleicanhydride having a molecular weight above about 1,000, such that aboutfifty per cent of the carboxyl groups of the acidic copolymer arereacted with said alcohols.

References Cited in the file of this patent UNITED STATES PATENTS NumberName Date 2,564,561 Carmichael Aug. 14, 1951 2,615,845 Lippencott et al.Oct. 28, 1952 2,634,256 Sparks et al Apr. 7, 1953 2,637,698 Tutwiler May5, 1953

1. A GREASE COMPRISING AN OLEAGINOUS VEHICLE AND A SALT IN AN AMOUNTSUFFICIENT TO THICKEN SAID VEHICLE TO FORM A GREASE, SAID SALT BEING AMETAL SALT OF AN ACIDIC REACTION PRODUCT OBTAINED BY REACTION OF ACOMPOUND SELECTED FROM THE GROUP CONSISTING OF AN ALIPHATIC MONOHYDRICALCOHOL HAVING AT LEAST ABOUT EIGHT CARBON ATOMS PER MOLECULE AND ANALIPHATIC MONOAMINE HAVING AT LEAST ABOUT EIGHT CARBON ATOMS PERMOLECULE, WITH AN ACIDIC COPOLYMER OF AN ALPHA, BETA UNSATURATEDPOLYCARBOXYLIC ACID AND A LOW MOLECULAR WEIGHT ORGANIC COMPOUND HAVING ATERMINAL VINYL GROUP AND HAVING LESS THAN ABOUT TEN CARBON ATOMS PERMOLECULE, SUCH THAT FROM ABOUT FIFTY TO ABOUT NINETY PER CENT OF THECARBOXYL GROUPS OF THE ACIDIC COPOLYMER ARE REACTED WITH SAID COMPOUND,SAID ACIDIC COPOLYMER HAVING A MOLECULAR WEIGHT ABOVE ABOUT 1,000, THEMETAL OF SAID SALT BEING SELECTED FROM THE GROUP CONSISTING OF METALS OFGROUPS I TRHOUGH III OF MENDELEEFF''S PERIODIC SYSTEM.